Esters of sulphonated aromatic carboxylic acids and peocess of making same



Patented Nov. 14, 1933 0 ESTERS 0F SULPHONATED AROMATIC OAR- BOXYLICACIDS ING SAME AND rnoonss or MAK- Friedrich Felix and om Albrecht,Basel, swam land, assignors to the firm of Society of Chemical Industryin Basle, Basel, Switzerland N'o Drawing. Application March 13, 1931,Serial No. 522,506, and in Switzerland March 29, 19cc 21 Claims.

The present invention relates to the manufacture of new esters ofsulphonated aromatic carboxylic acids. It comprises the process ofmaking these new esters, the new esters themselves, and the materialtreated with the new esters.

According to this invention new esters valuable as auxiliaries inindustry are made by the esterification or reaction of a sulphonic acidor a sulphonate of an aromatic dicarboxylic acid of the benzene andnaphthalene series or a substitution product thereof, an anhydride orhalide thereof, such as a sulphonic acid of phthalic acid,

isophthalic acid, naphthalic acid or an anhydride of one of these, thesulphoterephthalic acid, a sulpho -4-chlorophthalic acid, a-sulphophthalic acid-trichloride or the like, with a compound whichcontains hydroxyl groups bound to carbon atoms and more than two carbonatoms, and in which no atomis bound to oxygen atoms with more than twovalencies, or a derivative of such a compound.

The free sulphonicacid or its salts may be heated with the alcohol oralcohol-like compound for producing the esteriiication; in some caseshydrogen chloride gas, concentrated sulphuric acid or another agenttending to accelerate esterification may be present. The esterificationis facilitated if, in the course of the reaction, the water produced isremoved from the mixture in known manner, for example with the aid of amaterial which can form an azeotropic mixture with water. Instead ofstarting from a sulphonic vacid chloride,- the latter may be producedduringthe esterification, for example by use of phosphorus oxychlorideor the like. The sulphonic acid which is to be esterified need not bepure but may be in the form of the sulphonation mass obtained, asdescribed in'Swiss application No. 75,442 of 1930, by heating the parentmaterial with sulphuric anhydride under pressure and removing thegreater part of the excess of sulphonating agent used. Compoundscontaining hydroxyl groups suitable for the esteriflcation are monoandpoly-hydric saturated or unsaturated aliphatic alcohols with normalcarbon chains or branched chains and containing hydroxyl groups linkedto primary, secondary or tertiary carbon atoms, or derivatives of these,so far as they still contain a free hydroxyl group, for instanceisopropyl alcohol, butyl alcohol, amyl alcohol, octyl alcohol,diethylene-glycol, diethylene-glycolmono-ethylether, glycerin or thelike. There also come into consideration natural or synthetic higherfatty alcohols or alcohols derived from waxes, for instance cetylalcohol, stearyl alcohol,

oleyl alcohol or mixtures thereof; also oxidation products of aliphatichydrocarbons or alcohol-like. compounds or mixtures of such compoundsobtainable by catalytic hydrogenation; further, diacetone alcohol,hydrogenized final distillates of acetone or alcohols-which are obtainedby hydration of the-unsaturated hydrocarbons iormed by the crackingot-acid resin or the residual pitch from the distillation of allphaticraw materials. The alcohol to be esterlfied need not .be either in pureor in anhydrous condition; preferably naturally occurring orartificially produced mixtures are used, for example fusel oil, fuseloilirom sulphite spirit. or the commercial mixture of higher fattyalcohols; also suitable are aliphatic-aromatic alcohols, such as benzylalcohohfurther, phenols, cresols, naphthols, i. e. products containingconjugated don ble bonds, or the like, as well as their hydrogenated orpartially hydrogenated derivatives, such as cyclohexanol, methylhexalineand the like. Ammonia derivatives containing hydroxyl groups, such astriethanol-amine, may be used.- The esters may also be made from thederivatives of the compounds in question containing hydroxyl groups, forinstance from their oxides or halides. The latter are advantageouslycaused to react with the salts of the aromatic sulpho-dicarboxylicacids. Finally, the esters can be made by double decomposition, .forinstance by causing to react an ester of a lower alcohol with a higheralcohol.

The esters which are derived from the sulphonic acids of aromaticdicarboxylic acids 01' the benzene and naphthalene series or theirsubstitution products contain, on the one hand, the residues of thearomatic sulpho-dicarboxylic acids used and, on the other hand, residuesadhering to the carboxyl group of the general formula OR, wherein Rmeans the residues of the above mentioned compounds which containhydroxyl groups'bound to carbon atoms and more than two carbon atoms,and in which no atom is bound to oxygen atoms with more than twovalencies,

and which are free from heterocyclic rings.

They constitute, in the form of their dried alkali salts, colorless tolight-colored powders which easily dissolve in water, and which, whenheated -withsaponifylng agents, are split up into an aromaticsulpho-dicarboxylic acid and organic compounds containing hydroxylgroups. They have a pronounced tendency to assist wetting, cleansing andemulsiflcation. They therefore applicable in many ways in industry. fnu

The following examples illustrate the invention, the parts being byweight:

Example 1 In an autoclave phthalic acid-anhydride is converted intosulpho-phthalic acid anhydride by heating it for Several hours with 3molecular proportions of sulphuric acid anhydride to 140- 150 C., asdescribed in Swiss application No. 75,442 of 1930; with aid of a currentof dry air or by prolonged heating to 190-200 C., the excess ofsulphonating agent in the sulphonation mass is reduced to about 12 percent.

On to 176 parts of the sulphonation mass thus obtained there are droppedgradually, while stirring, at 50-65 C. 130 parts of amyl alcoholofboiling point 128-132 C.; the temperature of the mass is raised in thecourse of about 30 minutes to 120-122 C. After cooling the mixture isdiluted with ice, neutralized with a sodium hydroxide solution whilecooling and evaporated to dryness, preferably under diminished pressure.

There is thus obtained a somewhat grey powder, which dissolves freely inwater; the aqueous solution foams strongly when shaken and has apronounced wetting and emulsifying capacity. The product very probablyconstitutes a mixture of the two compounds 0000511 I COOCsHu NaOa andN110;

COOCsHi COONa Instead of amyl alcohol the equivalent quantity ofpurified butyl alcohol or purified secondary octyl alcohol may be used.it is advantageous to omit the heating to 120-122 C. and instead to stirthe mixture for some time at 50-60 C.

The working up may follow the above directions.

Example 2 NaO . Example 3 In a vessel having a stirrer and a refluxcondenser there is heated to boiling for a long time until reaction iscomplete, a mixture consisting of 20 parts of mono-sodiumphthalicacid-anhydride-p-sulphonate (which may be obtained for example byprolonged heating under pressure of the acid sodium salt of the phthalicacid-p-sulphonic acid obtained in the usual manner), 28.4 parts ofsulphite spirit fusel oil, 28.2

parts of benzene and 3 parts of concentrated hy-- drochloric acid. It isadvantageous that the reflux condensate should be'caused to pass inknown manner through a'water trap, so that the waterproduced by the.reaction may be continuously separated. If necessary, loss of benzene yIn both these casesoration should-be made good during the operation.After distilling the volatile matter, preferably in a vacuum, theproduct of esterification remains as a tough residue which is applicabledirectly as an auxiliary in the textile industry, for example as an aidin carbonizing.

Emam'ple4 In the apparatus described in the preceding 1 example 40.5parts of fusel oil and 40.5 parts of toluene are heated together untilthe aqueous layerinthe water trap no longer increases. There are thenadded 50 parts of the mono-sodium salt of sulphophthalic acid-anhydrideand the boiling is continued for about 24 hours. After there has beenadded a mixture of 34.4 parts of fusel oil and a like amount of toluene,the heating is further continued to boiling until the esterification iscomplete. After separating the volatile matters the esterificationmixture is obtained in the form of a solid, somewhat yellowish masswhich has properties similar to those of the product described inExample 1.

In a similar manner esterification with methylhexaline can be produced,in which case, however, it is not necessary to dehydrate the alcoholiccomponents as stated. There is thus obtained a bright yellow solidesterification product which has an excellent wetting efiect in water.

Example 5 22.8 parts of sulpho-phthalic-acid-anhydride and 25.6 parts ofthe usual conmiercial mixture of cetyland stearyl-alcohols, are stirredtogether at 50-'l0 C. until the mixture is homogeneous. The temperatureis then raised, while stirring, to 105 C. and the mass is allowed tocool. The product of esterification is treated with water, neutralizedand evaporated to dryness, whereby it is obtained as a feebly greypowder which yields with water when heated a nearly clear, slightlyopalescent" solution, which foams strongly when shaken. The product issuitable for use as a washing agent, for example in washing raw wool.

Example 6 obtained a grey-white powder, soluble in water to a clearsolution which strongly lowers surface tension of solutions such ascarbonizing acid.

Example 18.9 parts of 'l-chlorophthalic acid-anhydride' are convertedinto the sulphonic acid by heating them in a. closed vessel with 33.2parts'of sulphuric acid anhydride during 10 hours to 205- 210" C. Thegreater partof the sulphonating agent used in excess is then separatedby prolonged heating to 190-20090. 24.2 parts of the sulphonation masscontaining 21.3 parts of sulphochlorophthalic acid-anhydride are heatedwith 28;! parts of amyl alcohol on a boiling wateroccurred. .Afterhaving raised the temperature The product is a homogeneous liquid, whichis dissolved by water to a clear solution which foams strongly whenshaken. the liquid and evaporate it to dryness, whereby an easilypowdered, yellowish product is obbath lmtil practically completedissolution has quickly to 120" c. the whole is allowed to cool.

One may also neutralize I at the ordinary temperature in the liquor.

tamed which assists wetting in water or carbonizing acid.

In similar manner the sulphoterephthalic acid can be esterified withamyl alcohol by heating the sulphonation mass obtained from terephthalicacid and excess of sulphuric anhydride, as described above with amylalcohol, after the sulphonation mass has been substantially freed fromthe excess of the sulphonating agent. The

esterification product is a pale reddish-violet mass, easily pulverized,which is dissolved by water to a clear solution of high wettingcapacity.

Example 8 There is heated, while stirring, a mixture of 9.7 parts ofamyl alcohol and 13.9 parts of naphthalic acid-anhydride-B-sulphonicacid (the latter being obtainable from the free sulphonic acid byprolonged heating in a vacuum) for minutes at 115-120" C. Theesterification prodnot is a grey paste which is applicable directly orafter previous neutralization; it is dissolved by water to a clearsomewhat brownish yellow solution of high 'wetting capacity.

Forneutralization purposes there may be used 7 in this example, and alsoin the preceding examples, an organic base instead of caustic sodasolution or the like.

- The following examples illustrate the application of the productsobtainable according to the Examples 1' to 8:-

Example 9 by the acid and fall apart in the carbonizing process. Otherproducts behave in a simimr .manner, such as, for example, the estersfrom amyl alcohol or butyl alcohol and sulphophthalic acid.

Example 10 The ester from sulphophthalic acid and methylhexaline has inaqueous solution an unusually strong wetting capacity.. Thus even aconcentration of 1 gram per liter of this product determines the wettingof cotton in a very short time in a cold liquor. Woolen yarn, which isknown to be wetted with difficulty, sinks very rapidly Other esters,such as, for example, the amyl or butyl ester of the sulphophthalic acidhave also a very good wetting-out effect.

} Example 11 1/ There is prepared a mercerizing solution of B. whichcontains per liter 5 grams of the ester from sulphophthalic acid andfusel oil. In this solution raw cotton yarn or raw cotton fabrics may bemercerized directly without previous boiling or wetting.

Example 12 As is known, the dyeing throughout of fabrics or yarns whichare closely. woven or strongly twisted presents considerabledimculty.It'has been found that, for example in the case of vatdyestuffs,-- thethrough-dyeing can be essentially improved in the following manner:--

There is prepared a bath containing per liter of water 20 grams of thesodium salt of the ester from sulphophthalic acid and amyl alcohol, and

50 grams of Cibanone blue GCD double paste (cf. Supplement to the ColourIndex, page This suspension of dyestufi serves as an impregnating bathfor the material to be dyed through, which is padded therein severaltimes and then pressed. Afterwards the material thus impregnated istransferred to a fresh bath containing caustic soda solution andhydrosulphite, vatted in the usual manner, and then oxidized. A verygood through-dyeing is thus obtained.

Example 13 There is made a solution containing per liter of water 2grams of the ester from sulphophthalic acid and a mixture of cetyl andstearyl alcohol.

-In this solution greasy wool is washed at a temperature of C. in thecourse of A; hour. The bath may be used for several batches withoutfurther addition of the product and without marked diminution of itswashing power. The washing effect is very advantageous and the wool ispure white. As compared with soap the product has the advantage that itis stable towar lime and neutral in reaction.

Example 14 The ester of sulphophthalic acid and amyl alcohol may be usedwith advantage for the production of emulsions. Solutions of. 2 to 5 percent. strength of the product may be used and in these oils,particularly also solvents,- such as benzine and j benzene, maybeemulsified with ease. The emulsions of the -solvent s\can' be used withadvantage for cleaning textiles which have been stained with oils, fats,pitch, or the like.

For removing mineral oil spots from cotton fabrics, there is made anemulsion of, for example, grams 'of the above-named product, dissolvedin 1000 cc. of water, with 1000 cc. of benzene. This emulsion is dilutedwith water to 10000 cc. and the fabric to be cleaned is handled thereinduring 5 minutes. After washing and drying the oil spots disappearwithout leaving a residue. v

What we claim is:

1. A manufacture of esters of aromatic sulphodicarboxylic acids of thebenzene and naphthalene series by reaction of a member selected'from thegroup of compounds consisting of the aromatic sulphodicarboxylic acids,their salts, anhydrides and halides, with compounds which contain atleast one hydroxyl group bound to carbon atoms and more than two carbonatoms and in which no atom is bound to oxygen atoms with more than twovalencies.

2. A manufacture of esters of aromatic sulpho- -dicarboxylic acids ofthe benzene seriesby reaction of a member selected from the group ofcompounds, consisting of the aromatic sulphodicarboxylic. acids of thebenzene series, their action of a member selected from the group ofcompounds, consisting of the aromatic sulphoorthd-dicarboxylic acids ofthe benzene series,

their salts, anhydrides and halides, with compounds which contain atleast one hydroxyl group bound to carbonatoms and more than salts,anhydrides and halides, with compounds two carbon atoms and in which noatom is bound to oxygen atoms with more than two valencies.

4. A manufacture of esters of aromatic sulphodicarboxylic acids of thebenzene series by reaction of a member selected from the group ofcompounds, consisting of the sulphophthalic acid, its salts, anhydridesand halides, with compounds which contain at least one hydroxyl groupbound to carbon atoms and more than two carbon atoms and in which noatom is bound to oxygen atoms with more than two valencies.

5. A manufacture of esters of aromatic sulphodicarboxylic acids of thebenzene series by reaction of a member selected from the group ofcompounds, consisting of the sulphophthalic acid, its salts, anhydridesand halides, with organic compounds free from conjugated double bondswhich contain at least one hydroxyl group bound to carbon atoms and morethan two carbon atoms and in which no atom is bound to oxygen with morethan two valencies.

6. A manufacture of esters of aromatic sulphodicarboxylic acids of thebenzene series by reaction of a member selected from the group ofcompounds consisting of the sulphophthalic acid, its salts, anhydridesand halides, with organic compounds free from conjugated double bondswhich contain at least one hydroxyl group and more than four carbonatoms, and in which no atom is bound to oxygen atoms with more than twovalencies.

7. A manufacture of esters of aromatic sulphodicarboxylic acids of thebenzene series by reaction of a member selected from the group ofcompounds, consisting of the sulphophthalic acid, its salts, anhydridesand halides, with methylcyclohexanol.

8. A manufacture of esters of aromatic sulphodicarboxylic acids of thebenzene series by reaction of a member selected from the group ofcompounds, consisting of the sulphophthalic acid, its salts, anhydridesand halides, with aliphatic compounds which contain one hydroxyl groupbound to carbon atoms and more than two carbon atoms and in which noatom is bound to oxygen atoms with more than two valencies.

'9. A manufacture of esters of aromatic sulphodicarboxylic acids of thebenzene series by reaction of a member selected from the group ofcompounds, consisting of the sulphophthalic acid, its salts, anhydridesand halides, with amyl al cohol.

10. A manufacture of esters of aromatic sulatoms phodicarboxylic-acidsof the benzene series by reaction of a member selected from the group ofcompounds, consisting of the sulphophthalic acid, its salts, anhydridesand halides, with cetyl alcohol.

11. The esters containing, on the one hand, residues of an aromaticsulphodicarboxylie acid of the benzene and naphthalene series and, onthe other hand, residues adhering to the carboxyl group of the generalformula OR, wherein R means any organic residue which contains more thantwo carbon atoms and in which no atom is bound to oxygen atoms with morethan two valencies, and which is free from heterocyclic rings, whichproducts, in the form of their dried alkali salts, constitute colorlessto light-colored powders which easily dissolve in water, and which,when-: heated with saponifying agents, are split up into an aromaticsulphodicarboxylic acid and organic compounds containing hydroxylgroups.

12. The esters containing, on the one hand, residues of asulphodicarboxylic acid of the henzene series and, on the other hand,residues adhering to the carboxyl group of the general formula 0-3,wherein R means any organic residue which contains more than two carbonatoms and in which no atom is bound to oxygen atoms with more than twovalencies, and which is free from heterocyclic rings, which products, inthe form of their dried alkali salts, constitute colorless tolight-colored powders which easily dissolve in water, and which, whenheated with saponifying agents, are split up into a sulphodicarboxylicacid of the benzene series and organic compounds containing hydroxylgroups.

13. The esters containing, on the one hand, residues of asulpho-ortho-dicarboxylic acid of the benzene series and, on the otherhand, residues adhering to the carboxyl group of the general formulaO-R, wherein R means any organic residue which contains more than twocarbon atoms and in which no atom is bound to oxygen atoms with morethan two valencies, and which is free from heterocyclic rings, whichproducts, in the form of their dried alkali salts, constitute colorlessto light-colored powders which easily dissolve in water, and which, whenheated with saponifying agents, are split up into asulphoortho-dicarboxylic acid of the benzene series and organiccompounds containing hydroxyl groups.

14. The esters containing, on the one hand, residues adhering to thecarboxyl group of a sulphophthalic acid and, on the other hand, residuesadhering to the carboxyl group of the general formula OR, wherein Rmeans any organic residue which contains more than two carbon atoms andin which no atom is bound to oxygen atoms with more than two valencies,and which is free from heterocyclic rings, which products, in the formof their dried alkali salts, constitute colorless to light-coloredpowders which easily dissolve in water, and which, when heated withsaponifying agents, are split up into a sulphophthalic acid and organiccompounds containing sulphophthalic acid and, on the other hand,

residues adhering to the carboxyl group of the general formula 0R,wherein R means an organic residue free from conjugated double bondswhich contains more than two carbon atoms and in which no atom is boundto oxygen atoms with more than two valencies, and which is free fromheterocyclic rings, which products, in the form of their dried alkalisalts, constitute colorless to light-colored powders which easilydissolve in water, and which, when heated with saponifying agents, aresplit up into a sulphophthalic acid and organic compounds free fromconjugated double bonds containing hydroxyl groups.

16. The esters containing, on the one hand,

residues 'of a sulphophthalic acid and, on the other hand, residuesadhering to the carboxyl group of the general formula O--R, wherein Rmeans an organic residue free from conjugated double bonds whichcontainmore than four carbon atoms, and in which no atom is bound to oxygenatoms with more than two valencies, and which is free from heterocyclicrings, which products, in the form of their dried alkali salts,constitute colorless to light-colored powders hich easily dissolve inwater, and which, when heated with saponifying agents, are split up intoa sulphophthalic acid and organic compounds free from conjugated doublebonds containing hydroxyl groups.

17. The esters containing, on the one hand, residues of a sulphophthalicacid and, on the other hand, residues of the general formula OR, whereinR means a methyl-cyclohexyl residue, which products, in the form oftheir dried alkali salts, constitute colorless to light-colored powdersvwhich is free from heterocyclic rings, which products, in the form oftheir dried alkali salts, constitute colorless to light-colored powderswhich easily dissolve in water, and which, when heated with saponifyingagents, are split up into a sulphophthalic acid and aliphatic alcoholscontaining more than two carbon atoms.

19. The esters containing, on the one hand, residues adhering to thecarboxyl group of a sulphophthalic acid and, on the other hand, residuesadhering to the carboxyl group of the general formula OR, wherein Rmeans a saturated aliphatic residue which contains more than two carbonatoms and in which no atom is bound to oxygen atoms with more than twovalencies, and which is free from heterocyclic rings, which products, inthe form of their dried alkali salts, constitute colorless tolight-colored powders which easily dissolve in water, and'which, whenheated with saponifying agents, are split up into a sulphophthalic acidand saturated aliphatic alcohols containing more than two carbon atoms.

20. The esters containing, on the one hand, residues of a sulphophthalicacid and, on the other hand, OCsHu residues, which products. in the formof their dried alkali salts, constitute colorless to light-coloredpowders which easily dissolve in water, and which, when heated withsaponifying agents, are split up into a sulphophthalic acid and amylalcohols.

21. The esters containing, on the one hand, residues of a sulphophthalicacid and on the other hand, OCmHas residues, which products, in the formof their dried alkali salts, constitute colorless to light-coloredpowders which easily dissolve in water, and which, when heated withsaponifying agents, are split'up into a sulphophthalic acid and cetylalcohol.

mrnnmdn mm. 0110 ALBRECHT.

